CN107240683A - A kind of lithium titanate anode material and preparation method thereof - Google Patents
A kind of lithium titanate anode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to energy storage research field, more particularly to a kind of lithium titanate anode material, including nuclear structure and shell structure, the shell structure is uniformly wrapped on the nuclear structure surface, the nuclear structure particle diameter is D1, and the shell structure thickness is h1, contains graphene in the shell structure, the graphene sheet layer thickness h 2≤100nm, the graphene sheet layer planar diameter d1≤π * D1.So as to prepare the lithium titanate anode material of excellent electrochemical performance.
Description
Technical field
The invention belongs to energy storage material technical field, more particularly to a kind of lithium titanate anode material and preparation method thereof.
Background technology
Lithium ion battery is with its fast charging and discharging, low temperature performance well, specific energy is big, self-discharge rate is small, small volume, lightweight
Etc. advantage, since its birth, revolutionary change just is brought to energy storage field, is widely used in various portable electronics
In equipment and electric automobile.However as the improvement of people's living standards, higher Consumer's Experience is proposed to lithium ion battery
Higher requirement：More quick discharge and recharge (such as 5C even 10C), (such as subzero 30 is Celsius for broader temperature range
Degree) in use；The more excellent electrode material of new performance is had to look for solve the above problems.
Current commercialized lithium ion battery negative material is mainly graphite, but because of slow (the general charge and discharge of its charge/discharge rates
Electric speed is within 1C), and cryogenic property is poor (temperature in use is typically more than -10 DEG C), and the urgent of user can not be met
Demand；Therefore, more high charge-discharge speed, the negative material used in more wide temperature range exploitation it is extremely urgent.As lithium from
Sub- cell negative electrode material, lithium titanate receives much concern always：Its charge/discharge rates can be remained able in more than 10C, and at -30 DEG C
Ideal capacity has been given play to, therefore has been that one of optimal selection of negative material is filled soon by a new generation.
But it is due to that lithium titanate material particle electric conductivity itself is poor, it is larger to be assembled into the internal resistance of battery after battery, and
In charge and discharge process, easily produce gas to influence the use of battery, limit it and widely apply.It is above-mentioned in order to solve
Problem, prior art mainly has lithium titanate particle nanosizing or coated on lithium titanate anode material surface, is stablizing material
While expecting structure, moreover it is possible to obstruct lithium titanate material and directly contacted with electrolyte, it is to avoid battery is produced largely in cyclic process
Gas；So as to while cycle performance of battery is improved, solve the problems, such as lithium titanate battery aerogenesis.
Itself it is a kind of excellent covering material because grapheme material has unique flexible two-dimension plane structure,
Lithium titanate anode material surface can be coated on.But its two-dimentional lamellar structure is transmitted to ion inside and outside lithium titanate anode particle
During have obvious inhibition, so as to have influence on the performance of lithium titanate material dynamic performance.
In view of this, it is necessory to propose a kind of lithium titanate anode material and preparation method thereof, it can both give play to graphite
The sharpest edges of alkene, are avoided that it on influenceing transmission of the ion inside and outside lithium titanate material after lithium titanate material Surface coating again.
The content of the invention
It is an object of the invention to：In view of the shortcomings of the prior art, a kind of lithium titanate anode material provided, including core
Structure and shell structure, the shell structure are uniformly wrapped on the nuclear structure surface, and the nuclear structure particle diameter is D1, the shell
Structural thickness is h1, and graphene, 2≤100nm of the graphene sheet layer thickness h, the graphene film are contained in the shell structure
Layer plane diameter d1≤π * D1.So as to prepare the lithium titanate anode material of excellent electrochemical performance.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of lithium titanate anode material, including nuclear structure and shell structure, the shell structure are uniformly wrapped on the nuclear structure surface,
Characterized in that, the nuclear structure particle diameter is D1, the shell structure thickness is h1, contains graphene in the shell structure,
The graphene sheet layer thickness h 2≤100nm, the graphene sheet layer planar diameter d1≤π * D1, i.e., now, graphene sheet layer
At most the half region of nuclear structure is enveloped, transmission of the ion inside and outside lithium titanate anode material will not be completely enclosed.
Improved as one kind of lithium titanate anode material of the present invention, the nuclear structure is primary particle structure or second particle
Structure or multiple particle structure；Lithium titanate particle is included in the nuclear structure, non-lithium titanate particle, the non-titanium can also be included
Sour lithium particle includes native graphite, Delanium, carbonaceous mesophase spherules, soft carbon, hard carbon, petroleum coke, carbon fiber, thermal decomposed resins
At least one of carbon, silicon-carbon cathode material, alloy material of cathode.
Improved as one kind of lithium titanate anode material of the present invention, the π D1/3 of the graphene sheet layer planar diameter d1≤2,
When graphene coated is on primary particle surface, if the π D1/3 of d1=2, then ion is by graphene sheet layer edge-diffusion to graphite
Path during alkene lamella central area, is exactly equal to the path that ion is entered core central area by nuclear structure diffusion into the surface, now
Dynamic performance influence of the graphene sheet layer on lithium titanate anode material is smaller.
Improved as one kind of lithium titanate anode material of the present invention, in the clad, also include traditional clad or/
The polymer carbonization component obtained with monomer in situ polymerization.
Improved as one kind of lithium titanate anode material of the present invention, traditional clad is traditional clad raw material charing
Obtain；Traditional clad raw material is phenolic resin, melamine resin, Vinylidene Chloride, pitch, polyethylene, stearic acid, PVC, poly-
Acrylonitrile, natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers, polyethylene, polypropylene, polyamide, poly terephthalic acid
In glycol ester, nano cupric oxide, nano magnesia, nano-titanium oxide, nano aluminium oxide, nano-graphite, graphite flake at least
It is a kind of；The monomer includes esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, polyethylene glycol
Dimethylacrylate, polyethyleneglycol diacrylate, divinylbenzene, trimethylol-propane trimethacrylate, methyl
Methyl acrylate, N, N- DMAAs, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, butyl acrylate,
Positive Hexyl 2-propenoate, 2- cyclohexyl acrylates, dodecyl acrylate, GDMA, polyethylene glycol dimethyl
It is acrylate, polyethylene glycol dimethacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, four sweet
Alcohol diacrylate, tri (propylene glycol) diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation pentaerythrite
Acrylate, double-Glycerin tetraacrylate, pentaerythritol triacrylate, trimethylol propane trimethyl acrylic acid
Ester, glycerol propoxylate triacrylate, three（2- ethoxys）Isocyanuric acid triacrylate trimethylolpropane tris acrylic acid
Ester, propoxylation trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, the hydroxyl of ethoxylation three
In propane tri, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate at least
It is a kind of.
Present invention additionally comprises a kind of preparation method of lithium titanate anode material, mainly comprise the following steps：
Step 1, selection nuclear structural materials are standby；
Step 2, the clad slurry containing graphene sheet layer is prepared；
Step 3, nuclear structural materials described in step 1 are placed in the slurry that step 2 is obtained and coated, carbonization is carried out afterwards and is produced
To finished product lithium titanate anode material.
Improve, can also be included in the clad slurry as one kind of lithium titanate anode material preparation method of the present invention
Traditional clad raw material or/and polymer monomer.
As lithium titanate anode material preparation method of the present invention one kind improve, when in the clad contain polymer list
During body, after the step 3 cladding process, inducer need to be added and promote monomer in situ polymerization formation polymer, now, step
Three are：Nuclear structural materials described in step 1 are placed in the slurry that step 2 is obtained and coated, is subsequently placed in and is deposited with inducer
Environment in induce monomer in situ polymerization；Finally it is carbonized and obtains finished product lithium titanate anode material.The inducer is
Initiator, the initiator includes isopropyl benzene hydroperoxide, t-butyl hydrogen peroxide, cumyl peroxide, the spy of peroxidating two
The special butyl ester of butyl, dibenzoyl peroxide, dilauroyl peroxide, perbenzoic acid, peroxide tert pivalate ester, peroxidating
At least one of two diisopropyl carbonates, di-cyclohexylperoxy di-carbonate.
Improved as one kind of lithium titanate anode material preparation method of the present invention, the preparation described in step 2 contains graphene
During the clad slurry of lamella, surfactant can also be added, the surfactant includes the surface-active
Agent is that surfactant includes at least one of wetting agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent；It is described
Wetting agent is anionic or/and non-ionic wetting agent；The dispersant is fatty acid/aliphatic amide type/esters point
An at least class in powder, paraffin class, metal soap, low molecule wax class, HPMA；The bleeding agent is non-ionic or/and the moon
Ionic bleeding agent；The anionic wetting agents include alkyl sulfate, sulfonate, aliphatic acid or fatty acid ester sulfate,
At least one of carboxylic acid soaps and phosphate；The non-ionic wetting agent includes polyoxyethylated alkyl phenol, polyoxyethylene
At least one of fatty alcohol ether and polyoxyethylene polyoxypropylene block copolymer；The dispersant is vinyl stearic bicine diester
Amine, oleic acid acyl, glyceryl monostearate, glyceryl tristearate, atoleine, microcrystalline wax, barium stearate, zinc stearate,
At least one of calcium stearate, Tissuemat E and polyethylene glycol；The nonionic penetrant includes JFC, JFC-1, JFC-2
At least one of with JFC-E；The anionic bleeding agent comprising fast penetrant T, alkali-resistant penetrant OEP-70, alkaline-resisting ooze
Saturating at least one of agent AEP and seeping at high temperature agent JFC-M；The cosolvent includes benzoic acid, sodium benzoate, salicylic acid, water
At least one of poplar acid sodium, p-aminobenzoic acid, urethane, urea, acid amides, acetamide, borax and KI；It is described latent molten
Agent includes at least one of ethanol, glycerine, propane diols and polyethylene glycol.
Improved as one kind of lithium titanate anode material preparation method of the present invention, nuclear structural materials material described in step 1
The a diameter of D1 of grain, D1≤1 μm；Graphene sheet layer planar diameter d1 described in step 2≤π * D1.
The advantage of the invention is that：
1. the graphene coated structure of flexible, planar structure can be coated with significantly more efficient, be obstructed electrolyte and nuclear structure
Direct contact, improve material chemical property；
2.d1≤π D1 (smaller scope d1≤2 π D1/3) are that graphene sheet layer planar diameter is no more than the one of nuclear structure girth
Half, because the graphene of planar structure has inhibition to ion diffusion, but it is of the present invention compared with facet chi when using
During very little graphene, ion is smaller around row distance (distance of second particle radius length), therefore inhibition is faint, and lithium titanate is born
Pole material has excellent chemical property；
3. containing small molecule monomer in-situ polymerization component in clad, can effectively it improve inside clad between each component
Electronic conductance effect between connection effect, and clad and nuclear structure, because small molecule monomer is easier and other components
Infiltration, uniform mixing.
Embodiment
The present invention and its advantage are described in detail with reference to embodiment, but the embodiment party of the present invention
Formula not limited to this.
Comparative example, prepares the lithium titanate anode material that particle diameter is 12 μm；
It is prepared by step 1. nuclear structure：100nm lithium titanate particle is selected, pelletizing is carried out after uniformly being mixed with conductive carbon, is obtained
The second particle nuclear structure of a diameter of about 12 μm of grain is stand-by；
Step 2., as covering material, is coated to the nuclear structure that step 1 is prepared, is carbonized afterwards, obtained from pitch
Particle diameter is 12 μm of lithium titanate anode material.
Embodiment 1, is that the present embodiment comprises the following steps with comparative example difference：
It is prepared by step 1. nuclear structure：100nm lithium titanate particle is selected, pelletizing is carried out after uniformly being mixed with conductive agent component, obtains
It is stand-by to the second particle nuclear structure that particle diameter is about 12 μm；
Step 2, clad slurry is prepared：Pitch is heats liquefied；By the scattered of a diameter of 37.68 μm of graphene uniform of lamella
In nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain clad raw material；
Step 3, nuclear structural materials described in step 1 are placed in the clad raw material that step 2 is obtained and coated, carbon is carried out afterwards
Change and obtain finished product lithium titanate anode material.
Embodiment 2, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；By the scattered of a diameter of 25.12 μm of graphene uniform of lamella
In nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain clad raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 3, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；By being dispersed in for a diameter of 15 μm of graphene uniform of lamella
In nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain clad raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 4, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；By being dispersed in for a diameter of 5 μm of graphene uniform of lamella
In nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain clad raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 5, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；By being dispersed in for a diameter of 1 μm of graphene uniform of lamella
In nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain clad raw material；
It is other identical with embodiment 1, it is not repeated herein.
Embodiment 6, difference from Example 1 is, the present embodiment comprises the following steps：
Step 2, clad slurry is prepared：Pitch is heats liquefied；By being dispersed in for a diameter of 0.2 μm of graphene uniform of lamella
In nmp solvent, add afterwards in pitch；It is uniformly mixing to obtain clad raw material；It is other identical with embodiment 1, here no longer
Repeat.
Embodiment 7, difference from Example 1 is, the present embodiment comprises the following steps：
Step 1, prepared by nuclear structure：100nm lithium titanate particle is selected, pelletizing is carried out after uniformly being mixed with conductive agent component, obtains
It is stand-by to the second particle nuclear structure that particle diameter is about 12 μm；
Step 2, clad slurry is prepared：By trimethylol-propane trimethacrylate and the graphene of a diameter of 5 μm of lamella
Mediated, after being well mixed；It is well mixed afterwards with phenolic resin and obtains clad slurry；
Step 3, nuclear structural materials described in step 1 are placed in the clad slurry that step 2 is obtained and coated, is placed in afterwards
In BPO solution, promote monomer to carry out in-situ polymerization generation polymer, the polymer of generation by inside clad, clad with
It is closely joined together between nuclear structure；Finally it is carbonized and obtains finished product lithium titanate anode material.
It is other identical with comparative example 1, it is not repeated herein.
Embodiment 8, prepares the lithium titanate anode material that particle diameter is 100 μm；
Step 1：It is prepared by nuclear structure, selection particle diameter is 200nm lithium titanate, Delanium hybrid particles as primary particle, its
Middle metatitanic acid lithium content is 90%；CNT, super conductive carbon mix are conductive agent component；By neopelex, one
Secondary particle mixing, adds a small amount of N, N- dimethyl pyrrolidone solution is mediated, and obtains primary particle dispersed afterwards
Slurry；Conductive agent, PVP are mixed, a small amount of N is added afterwards, N- dimethyl pyrrolidone solution is mediated, and obtains graphene equal
Even scattered slurry；Two kinds of slurries are uniformly mixed, pelletizing obtains nuclear structure afterwards；
Step 2, clad slurry is prepared：Lamellar spacing is mixed into for graphene, PVP, NMP of a diameter of 5 μm of 100nm lamellas
Row is mediated, after being well mixed；It is well mixed afterwards with phenolic resin and obtains clad slurry；
It is other identical with comparative example 1, it is not repeated herein.
Battery is assembled：It is lithium titanate anode material and conductive agent that comparative example, embodiment 1- embodiments 8 are prepared, viscous
Connect agent, stirring solvent and obtain electrode slurry, apply form negative electrode on a current collector afterwards；By negative electrode and anode electrode
The assembling of (cobalt acid lithium is active material), barrier film obtains naked battery core, and bag is entered afterwards and carries out top side seal, drying, fluid injection, standing, change
Resultant battery is obtained into, shaping, degasification.
Material properties test：
Gram volume is tested：Lithium titanate material in each embodiment and comparative example is prepared by following flow in 25 DEG C of environment
Battery core carries out gram volume test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand 3min；1C is permanent
Stream is discharged to 1.5V, obtains discharge capacity D1；Stand 3min；1C constant-current charges are to 2.35V；Completion capacity is surveyed after standing 3min
The weight of lithium titanate material, that is, obtain negative pole gram volume, acquired results are shown in Table 1 in examination, D1 divided by negative electricity pole piece.
Inner walkway：Lithium titanate material in each embodiment and comparative example is prepared by following flow in 25 DEG C of environment
Battery core carry out inner walkway：Stand 3min；1C constant-current charges are to 2.35V, 2.35V constant-voltage charges to 0.1C；Stand 3min；Again
Using electrochemical workstation, the DCR values of battery core are tested, acquired results are shown in Table 1.
High rate performance is tested：Each embodiment and comparative example lithium titanate material are prepared into by following flow in 25 DEG C of environment
The battery core arrived carries out high rate performance test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand
3min；0.5C constant-current discharges obtain discharge capacity D1 to 1.5V；Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges
To 0.1C；Stand 3min；5C constant-current discharges obtain discharge capacity D2 to 1.5V；Stand 3min；High rate performance is completed afterwards to survey
Examination, battery high rate performance=D2/D1*100%, acquired results are shown in Table 1.
Loop test:Each embodiment and comparative example lithium titanate material are prepared by following flow in 25 DEG C of environment
Battery core carry out loop test：Stand 3min；1C constant-current charges are to 2.8V, 2.8V constant-voltage charges to 0.1C；Stand 3min；1C is permanent
Stream is discharged to 1.5V, obtains discharge capacity D1；Stand 3min, " 1C constant-current charges to 2.8V, 2.8V constant-voltage charges to 0.1C；It is quiet
Put 3min；1C constant-current discharges obtain discharge capacity Di to 1.5V；Stand 3min " to repeat to obtain D1000 999 times, complete to follow afterwards
Ring test, calculating capability retention is D1000/D1*100%, and acquired results are shown in Table 1.
Gas production is evaluated：The above-mentioned battery outward appearance for finishing loop test of observation, judge its gas production number.It the results are shown in Table
1。
Battery core gram volume, circulation volume conservation rate and high rate performance that table 1, different lithium titanate anode materials are prepared
It can be obtained by table 1, lithium titanate anode material prepared by the present invention, with more outstanding chemical property：I.e. higher gram
Capacity, more preferable circulation volume conservation rate and higher high rate performance and smaller internal resistance and less circulation aerogenesis.
Specifically, comparative examples can be obtained with embodiment 1- embodiments 6, with the reduction of clad graphene sheet layer, gram appearance of material
Amount first increase, rear holding are stable, and DCR is gradually reduced, and cycle performance has attenuation trend, high rate performance to gradually step up, aerogenesis problem
It is basic to solve, because after graphene sheet layer reduces, it is reduced to the inhibition that ion is transmitted, but covered effect has variation
Trend (when i.e. graphene sheet layer is too small, it is impossible to which contact of the barrier electrolyte with nuclear structure completely is so as to occurring side reaction).By
Each embodiment can be obtained, and the present invention has universality, be adapted to various lithium titanate anode materials and preparation method thereof.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in above-mentioned embodiment, every those skilled in the art exist
Made any conspicuously improved, replacement or modification belong to protection scope of the present invention on the basis of the present invention.This
Outside, although having used some specific terms in this specification, these terms merely for convenience of description, not to the present invention
Constitute any limitation.
Claims (10)
1. a kind of lithium titanate anode material, including nuclear structure and shell structure, the shell structure are uniformly wrapped on the nuclear structure
Surface, it is characterised in that the particle diameter of the nuclear structure is D1,
Contain graphene in the shell structure, lamellar spacing h2≤100nm of the graphene,
The slice plane diameter d1 of the graphene≤π * D1.
2. the lithium titanate anode material described in a kind of claim 1, it is characterised in that the nuclear structure be primary particle structure or
Lithium titanate component is included in second particle structure, the nuclear structure.
3. a kind of lithium titanate anode material described in claim 1, it is characterised in that the slice plane diameter d1 of the graphene
≤2πD1/3。
4. the lithium titanate anode material described in a kind of claim 1, it is characterised in that in the shell structure, also includes cladding
The polymer carbonization component layers that layer or/and monomer in situ polymerization are obtained.
5. the lithium titanate anode material described in a kind of claim 4, it is characterised in that the clad is traditional clad raw material
Charing is obtained；Traditional clad raw material be phenolic resin, melamine resin, Vinylidene Chloride, pitch, polyethylene, stearic acid,
It is PVC, polyacrylonitrile, natural rubber, butadiene-styrene rubber, butadiene rubber, EP rubbers, polyethylene, polypropylene, polyamide, poly- to benzene
In naphthalate, nano cupric oxide, nano magnesia, nano-titanium oxide, nano aluminium oxide, nano-graphite, graphite flake
At least one；The monomer includes esters of acrylic acid, methyl acrylic ester, styrene, acrylonitrile, methacrylonitrile, poly-
Ethylene glycol dimethacrylate, polyethyleneglycol diacrylate, divinylbenzene, trimethylol propane trimethyl acrylic acid
Ester, methyl methacrylate, N, N- DMAAs, N- acryloyl morpholines, methyl acrylate, ethyl acrylate, propylene
Acid butyl ester, positive Hexyl 2-propenoate, 2- cyclohexyl acrylates, dodecyl acrylate, GDMA, polyethylene glycol
Dimethylacrylate, polyethylene glycol dimethacrylate, neopentylglycol diacrylate, 1,6-HD diacrylate
Ester, tetraethylene glycol diacrylate, tri (propylene glycol) diacrylate, ethoxyquin tetramethylol methane tetraacrylate, the third oxidation
Pentaerythritol acrylate, double-Glycerin tetraacrylate, pentaerythritol triacrylate, trimethylolpropane tris first
Base acrylate, glycerol propoxylate triacrylate, three（2- ethoxys）Isocyanuric acid triacrylate trimethylolpropane tris
Acrylate, propoxylation trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethyoxyl
Change in trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, tetramethylol methane tetraacrylate
At least one.
6. the preparation method of the lithium titanate anode material described in a kind of claim 1, it is characterised in that main to include following step
Suddenly：
Step 1, selection nuclear structural materials are standby；
Step 2, the clad slurry containing graphene sheet layer is prepared；
Step 3, nuclear structural materials described in step 1 are placed in the slurry that step 2 is obtained and coated, carbonization is carried out afterwards and is produced
To finished product lithium titanate anode material.
7. the preparation method of the lithium titanate anode material described in a kind of claim 6, it is characterised in that in the clad slurry
Also include clad raw material or/and polymer monomer.
8. the preparation method of the lithium titanate anode material described in a kind of claim 7, it is characterised in that contain when in the clad
When having polymer monomer, after the step 3 cladding process, inducer need to be added and promote monomer in situ polymerization formation polymerization
Thing.
9. a kind of preparation method of the lithium titanate anode material described in claim 6, it is characterised in that the preparation described in step 2
During clad slurry containing graphene sheet layer, surfactant is additionally added, the surfactant includes wetting
At least one of agent, dispersant, bleeding agent, solubilizer, cosolvent, cosolvent.
10. a kind of preparation method of the lithium titanate anode material described in claim 6, it is characterised in that nuclear structure described in step 1
Particle diameter D1≤1 μm of material；The planar diameter d1 of graphene sheet layer described in step 2≤π * D1.
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| CN102468485A (en) * | 2010-11-04 | 2012-05-23 | 海洋王照明科技股份有限公司 | Lithium titanate composite material, preparation method thereof, and application thereof |
| CN102820461A (en) * | 2012-08-20 | 2012-12-12 | 上海交通大学 | Method for preparing carbon-coated nano-lithium titanate by ethylene diamine tetraacetic acid-citric acid (EDTA-CA) joint complexation |
| CN106299309A (en) * | 2016-09-30 | 2017-01-04 | 上海交通大学 | Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof |
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| CN102468485A (en) * | 2010-11-04 | 2012-05-23 | 海洋王照明科技股份有限公司 | Lithium titanate composite material, preparation method thereof, and application thereof |
| CN102820461A (en) * | 2012-08-20 | 2012-12-12 | 上海交通大学 | Method for preparing carbon-coated nano-lithium titanate by ethylene diamine tetraacetic acid-citric acid (EDTA-CA) joint complexation |
| CN106299309A (en) * | 2016-09-30 | 2017-01-04 | 上海交通大学 | Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof |
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